Stabilized fluoroolefin refrigerant compositions and methods for their production, storage and usage

ABSTRACT

The present invention relates to refrigerant compositions comprising at least one fluoroolefin, at least one lubricant and an effective amount of at least one inhibitor wherein the inhibitor is present in the fluoroolefin and the lubricant.

This Application claims the benefit of Application No. PCT/2019/02977,filed on Apr. 30, 2019. The disclosure of PCT/2019/02977 is herebyincorporated by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates broadly to stabilized refrigerantcompositions comprising at least one fluoroolefin, at least onelubricant and at least one inhibitor comprising at least one memberselected from the group consisting of limonene, α-terpinene,α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol,benzene-1,4-diol wherein the inhibitor is present in a liquidfluoroolefin as well as the lubricant.

2. Description of Related Art

New environmental regulations on refrigerants have forced therefrigeration and air-conditioning industry to look for new refrigerantswith low global warming potential (GWP).

Replacement refrigerants are being sought that have low GWP, notoxicity, non-flammability, reasonable cost and excellent refrigerationperformance.

Fluoroolefins have been proposed as refrigerants, alone or in mixtures.These products have been extensively tested for chemical stability andcompatibility with materials typically used in air conditioning orrefrigeration systems (ref. “1234yf—A Low GWP Refrigerant For MAC,Honeywell/DuPont Joint Collaboration” presentation to JAMA/JARIA, Oct.3, 2007) and shown to be stable under typical operating conditions.However, it has been observed that certain fluoroolefins can exhibitdegradation and/or produce unwanted by-products under abnormalconditions such as extreme temperatures or contact with other compoundsin a contaminated system (e.g., excessive oxygen, oxidizing chemicals,or radical generating compounds, among various contaminants) that mightoccur unexpectedly in a particular use and/or application. Suchdegradation may occur when fluoroolefins are utilized as refrigerants orheat transfer fluids. This degradation may occur by any number ofdifferent mechanisms. Examples of stabilized refrigerant compositionsare disclosed in JP 2009298918; U.S. Pat. Nos. 6,969,701; 8,133,407; US2006/0022166; US 2006/0043330; US 2008/0157022; and WO 2007/126760 aswell as EP 2057245; U.S. Pat. Nos. 8,101,094; 8,535,555; 8,097,181; and8,075,796; the disclosure of which is hereby incorporated by reference.

Under certain abnormal conditions and in the presence of undesiredcontaminants that could function as an initiator, fluoroolefins mayoligomerize or homopolymerize in the presence of certain contaminantsthat may be present. Accordingly, there is a need in this art forstabilized fluoroolefin containing refrigerant compositions havingreduced, if not eliminated potential to oligomerize or homopolymerize.

SUMMARY OF THE INVENTION

The instant invention can solve problems associated with polymerizationinitiation by providing at least one inhibitor that is present in aliquid fluoroolefin as well as a lubricant. In particular, the presentinvention can improve the ability of hydrofluoroolefin containingrefrigerant composition to withstand abnormal conditions, and alsosolves potential problems associated with initiators (e.g.,contaminants) causing a fluoroolefin (e.g., tetrafluoropropene) tooligomerize or homopolymerize, by adding at least one inhibitor to afluoroolefin containing composition. By “inhibitor” it is meant to referto at least one compound in accordance with the present invention thatreduces, if not eliminates, conversion of hydrofluoroolefins intooligomers or polymers. While oligomerization or homopolymerizationreactions may be accelerated by relatively high temperatures, suchreactions may also occur under ambient conditions depending upon theconcentration and type of initiator (e.g., contaminant). The inhibitorcan function as a radical inhibitor and without affecting therefrigeration performance or compatibility of the refrigerantcomposition with refrigerant oil and parts. The stabilized refrigerantcompositions may be useful in cooling systems and as replacements forexisting refrigerants with higher global warming potential.

To avoid possible instability of the fluoroolefins, it has been foundthat adding certain inhibitor compounds, namely hydrocarbons comprisingat least one of cyclic monoterpene; lipophilic organic compoundsincluding tocopherols such as α-Tocopherol; phenols, aromatic organiccompounds having at least one chemical moiety C₆H₄(OH) includingbenzene-1,4-diol, to fluoroolefin containing refrigerant compositionswill increase the stability thereof during packaging, storage and usagein refrigeration or air-conditioning system applications. Specificexamples of inhibitor compounds comprise at least one member selectedfrom the group consisting of limomene, α-terpinene, α-Tocopherol,Butylated hydroxytoluene, 4-Methoxyphenol, Benzene-1,4-diol. In oneembodiment of the invention, the inventive inhibitor compositioncomprises a liquid at a temperature from about −100 to about 220° C.,about −90 to about 200° C. and in some cases about −80 to about 185° C.

In one particular embodiment, the invention relates to fluoroolefincontaining refrigerant compositions comprising an inhibitor that caninteract or react with O₂ and fluoroolefin polyperoxides and in turninhibit or preclude reaction of such compounds with a hydrofluorolefin.Examples of such an inhibitor comprise at least one of limonene andα-terpinene. Limonene and α-terpinene have the following structures:

In one embodiment of the invention, the inhibitor comprises α-terpinene.Without wishing to be bound by any theory or explanation, it is believedthat due to the presence of the conjugated double bond in its structure,α-terpinene can form an aromatic ring upon oxidation.

In one embodiment of the invention, limonene or α-terpinene optionallywith an antioxidant has unique fragrant even at a few ppm level. Thispleasant odor can be utilized for refrigerant leakage detection withrefrigerant and blends based on hydrofluoroolefins (e.g., comprising atleast one of 1234yf, 1234ze and combinations thereof). This isespecially beneficial for early refrigerant leakage detection inhousehold air conditioner or mobile air conditioner as paraprofessionalelectronic leak detectors often are not available in either location.

One embodiment of the invention relates to a refrigerant compositioncomprising:

-   -   a. at least one fluoroolefin;    -   b. at least one lubricant; and    -   c. an effective amount of at least one inhibitor comprising:        hydrocarbons comprising cyclic monoterpene; lipophilic organic        compounds including tocopherol including α-Tocopherol; phenols,        aromatic organic compounds having the chemical formula C₆H₄(OH)        including benzene-1,4-diol; wherein the inhibitor is present in        a liquid fluoroolefin as well as the lubricant.

One embodiment of the invention relates to any of the foregoingrefrigerant compositions and further comprising at least oneanti-oxidant. While any suitable oxidant can be employed, examples ofsuitable oxidants comprise at least one member selected from the groupconsisting of butylated hydroxytoluene, butylated hydroxyanisole,tertiary-butylhydroquinone, gallate, 2-phenyl-2-propanol,1-(2,4,5-trihydroxyphenyl)-1-butaone, bisphenol methane derivatives,2,2′-methylene bis (4-methyl-6-t-butyl phenol), among other phenolics,and combinations thereof.

One particular embodiment relates to using the foregoing anti-oxidantswith an inhibitor comprising at least one of limonene and α-terpinene.

Another embodiment of the invention relates to a method for stabilizinga refrigerant composition comprising at least one fluoroolefin, saidmethod comprising adding an effective amount of at least one inhibitorwherein the inhibitor is a hydrocarbon comprising at least one memberselected from the group consisting of cyclic monoterpene; lipophilicorganic compounds including tocopherol including α-Tocopherol; phenols,and aromatic organic compounds having the chemical formula C₆H₄(OH)including benzene-1,4-diol, and mixtures thereof, to said compositioncomprising at least one fluoroolefin.

Another embodiment of the invention relates to a method for reducingoligomerization or homopolymerization of a refrigerant compositioncomprising at least one fluoroolefin, which is caused by the presence ofan inadvertent or undesired contaminant present in at least one ofconduits, lines and other systems used for handling the fluoroolefincontaining refrigerant compositions; packaging (containers), and arefrigeration, air-conditioning or heat pump system, said methodcomprising adding an inhibitor comprising at least one hydrocarbonscomprising cyclic monoterpene; lipophilic organic compounds includingtocopherol including α-Tocopherol; phenols, aromatic organic compoundshaving the chemical formula C₆H₄(OH) including benzene-1,4-diol, andmixtures thereof, to at least one of said system, container andcomposition comprising at least one fluoroolefin.

A further embodiment of the invention relates to a fluoroolefincontaining refrigerant composition within a container wherein thefluoroolefin has a reduced potential to oligomerize or homopolymerize incomparison to refrigerant compositions without the inventive inhibitorcomposition.

One embodiment of the invention relates to a refrigerant compositioncomprising at least one fluoroolefin and an effective amount of at leastone inhibitor and wherein the composition is substantially free ofoligomeric, homopolymers or other polymeric products derived from thefluoroolefin.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the composition comprises less thanabout 0.03 wt. % of oligomeric, homopolymers or other polymericproducts.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions and further comprising at least one memberselected from the group consisting of air, oxygen, cumene hydroperoxide,and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates,percarbonates, perborates and hydropersulfatees.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the inhibitor comprises at least onemember selected from the group consisting of limomene, α-terpinene,α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol,benzene-1,4-diol.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the fluorolefin comprises at least onemember of HFO-1234yf and HFO-1234ze.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions and further comprising at least one memberselected from the group consisting of HFC-32, HFC-125, HFC-134a,HFC-152a, HFC-227ea and carbon dioxide.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions and further comprising at least one memberselected from the group consisting of HFC-134a, HFO-1243zf, HFO1225ye,HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-244bb andHFC-245cb.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions and further comprising at least one memberselected from the group consisting of HCC-40, HCFC-22, CFC-115,HCFC-124, HCFC-1122, and CFC-1113.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the inhibitor is present in an amountof about 30 to about 3,000 ppm.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions and further comprising at least one memberselected from the group consisting of butylated hydroxytoluene,butylated hydroxyanisole, tertiary-butylhydroquinone, gallate,2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butaone, phenolics,bisphenol methane derivatives, and 2,2′-methylene bis(4-methyl-6-t-butyl phenol).

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the inhibitor comprises at least one oflimonene and α-terpinene.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the inhibitor comprises a liquid at atemperature of about −80 to 180° C.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions and optionally further comprising at least oneantioxidant.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions and further comprising at least one memberselected from the group consisting of HFO-1225yeZ, HFO-1243zf,HFO-1234ze, HFC-236ea, HFC-245fa, and 3,3,3-trifluoropropyne.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the member comprises HFO-1234ze,HFO-1225yeZ and 3,3,3-trifluoropropyne.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the composition is substantially freeof at least one of ammonia and CF3I.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the composition consists essentially ofHFO-1234yf and limonene and does not contain ammonia or CF3I.

Another embodiment of the invention relates to any of the foregoingrefrigerant compositions wherein the composition consists essentially ofHFO-1234yf, 3,3,3-trifluoropropyne and limonene.

One embodiment of the invention relates to a method for reducingformation of oligomers and homopolymers comprising contacting arefrigerant composition comprising at least one fluroolefin with anamount of at least one member selected from the group consisting oflimomene, α-terpinene, α-tocopherol, butylated hydroxytoluene,4-methoxyphenol, and benzene-1,4-diol, that is effective to reduceoligomer or homopolymer formation.

Another embodiment of the invention relates to any of the foregoingmethods wherein the refrigerant composition has been exposed to at leastone member selected from the group consisting of air, oxygen, cumenehydroperoxide, and fluoroolefin polyperoxides, peroxides,hydroperoxides, persulfates, percarbonates, perborates andhydropersulfatees before said contacting.

Another embodiment of the invention relates to any of the foregoingmethods that employs any of the foregoing refrigerant compositions forheating or cooling.

Another embodiment of the invention relates to a container with arefrigerant comprising any of the foregoing refrigerant compositions.

The embodiments of the invention can be used alone or in combinationswith each other, and that different embodiments can be combined and formpart of the invention.

BRIEF SUMMARY OF THE DRAWINGS

FIG. 1 is a graphical representation of NRTL fit to experimental VLE ofR-1234yf/lubricant.

FIG. 2 is a graphical representation of NRTL fit to experimental VLE ofR-1234yf/d-limonene.

FIG. 3 is a graphical representation of an expanded view ofR-1234yf-rich domain of R-1234yf/d-limonene showing negative deviationsfrom Raoult's Law.

FIG. 4 is a graphical representation of NRTL fit using calculatedd-limonene/POE32-3MAF VLE data.

FIG. 5 is a graphical representation of a ternary VLLE calculation ofR-1234yf/1000 ppm d-limonene/POE32-3MAF.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a stabilized refrigerant compositioncomprising at least one fluoroolefin, at least one lubricant and aneffective amount of at least one inhibitor wherein the inhibitor ispresent in a liquid fluoroolefin as well as the lubricant. By“stabilized” it is meant to refer to a composition comprising aneffective amount of at least one inhibitor compound that inhibits, ifnot eliminates a fluoroolefin from interacting with another compound andforming dimers, oligomers, homopolymers or polymeric products. Examplesof such compounds that can cause such interactions include oxidizerssuch as air, oxygen, cumene hydroperoxide, and fluoroolefinpolyperoxides, peroxides, hydroperoxides, persulfates, percarbonates,perborates. hydropersulfatees among other initiators. Initiatorcompounds can be present in an amount from about 10 to about 15,000 ppmby weight, about 1,000 to about 10,000 ppm and in some cases about 1,000to about 3,000 ppm and in some embodiments 30 to 2,000 ppm. Suchinitiator compounds can be present as contaminants in at least one ofconduits, lines and other systems used for handling the fluoroolefincontaining refrigerant compositions; packaging (containers), and arefrigeration, air-conditioning or heat pump system. Without wishing tobe bound by any theory or explanation it is believed that certaincontaminants can function as radical initiators thereby causing thefluoroolefin to oligomerization, homopolymerization or form otherpolymeric products.

In one embodiment of the invention, the inventive refrigerantcompositions are substantially free of oligomeric, homopolymers or otherpolymeric products derived from a hydrofluoroolefin. By “substantiallyfree” it is meant that the composition contains less than about 1 wt %,less than about 0.07 wt %, less than about 0.03 wt % and in some casesabout 0 ppm of such products when measured by IR or NMR In anotherembodiment of the invention, the inventive refrigerant compositions aresubstantially free of certain conventional inhibitor compounds includingsesquiterpene compounds such as at least one member selected from thegroup consisting of famesol, famesene; ionic liquids such as an ionicliquid comprising an anion selected from the group consisting of[CH₃CO₂]⁻, [HSO₄]⁻, [CH₃OSO₃]⁻, [C₂H₅OSO₃]⁻, [AlC₄]⁻, [CO₃]²⁻, [HCO₃]⁻,[NO₂]⁻, [NO₃]⁻, [SO₄]²⁻, [PO₄]³⁻, [HPO₄]²⁻, [H₂PO₄]⁻, [HSO₃], andcertain fluorinated anion wherein the fluorinated anion is selected fromthe group consisting of [BF₄]⁻, [PF₆]⁻, [SbF₆]⁻, [CF₃SO₃]⁻,[HCF₂CF₂SO₃]⁻, [CF₃HFCCF₂SO₃]⁻, [HCCIFCF₂SO₃]⁻, [(CF₃SO₂)₂N]⁻,[(CF₃CF₂SO₂)₂N]⁻, [(CF₃SO₂)₃C]⁻, [CF₃CO₂]⁻, [CF₃OCFHCF₂SO₃]⁻,[CF₃CF₂OCFHCF₂SO₃]⁻, [CF₃CFHOCF₂CF₂SO₃]⁻, [CF₂HCF₂OCF₂CF₂SO₃]⁻,[CF₂ICF₂OCF₂CF₂SO₃]⁻, [CF₃CF₂OCF₂CF₂SO₃]⁻, [(CF₂HCF₂SO₂)₂N]⁻,[(CF₃CFHCF₂SO₂)₂N]⁻ and mixtures thereof. By substantially free it ismeant that the inventive refrigerant compositions contains less thanabout 500 ppm, typically less than about 250 ppm, in some cases about100 ppm and in some cases about 0 ppm of such conventional inhibitors

The inventive refrigerant compositions have a variety of utilities heattransfer mediums (such as heat transfer fluids and refrigerants for usein refrigeration systems, refrigerators, air conditioning systems, heatpumps, chillers, and the like), among others. The inventive compoundsare particularly suited for use in mobile air conditioning systems andas a component for making a refrigerant blend for use in stationary heattransfer systems.

A heat transfer medium (also referred to herein as a heat transferfluid, a heat transfer composition or a heat transfer fluid composition)is a working fluid used to carry heat from a heat source to a heat sink.

A refrigerant is a compound or mixture of compounds that function as aheat transfer fluid in a cycle wherein the fluid undergoes a phasechange from a liquid to a gas (or vapor) and back. The inhibitor ispresent in at least the liquid fluoroolefin containing phase of therefrigerant as well as a lubricant component of the refrigerant. In oneembodiment, about 10 to about 80 wt %, about 25 to about 75 wt % and, insome cases, about 45 to about 60 wt % of the inhibitor is present in theliquid fluoroolefin phase with the remainder predominantly present inthe lubricant phase. In one embodiment, the vapor phase is substantiallyfree of inhibitor. By “substantially free” it is meant that the amountof inhibitor in the vapor fluoroolefin phase is less than about 10 ppm,in some cases less than about 5 and typically less than about 2 ppm. Inone embodiment, the refrigerant comprises a vapor phase comprising atleast one fluoroolefin and a liquid phase comprising at least onefluorolefin, at least one lubricant and at least one inhibitor and insome cases wherein the vapor phase is substantially free of theinhibitor.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a composition,process, method, article, or apparatus that comprises a list of elementsis not necessarily limited to only those elements but may include otherelements not expressly listed or inherent to such composition, process,method, article, or apparatus. Further, unless expressly stated to thecontrary, “or” refers to an inclusive or and not to an exclusive or. Forexample, a condition A or B is satisfied by any one of the following: Ais true (or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistsof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause, other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition, method that includes materials, steps, features,components, or elements, in addition to those literally disclosedprovided that these additional included materials, steps, features,components, or elements do materially affect the basic and novelcharacteristic(s) of the claimed invention, especially the mode ofaction to achieve the desired result of any of the processes of thepresent invention. The term “consisting essentially of” occupies amiddle ground between “comprising” and “consisting of.”

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso include such an invention using the terms “consisting essentiallyof” or “consisting of.”

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

The term fluoroolefin, as used herein, describes compounds whichcomprise carbon atoms, fluorine atoms, and optionally hydrogen atoms. Inone embodiment, the fluoroolefins used in the refrigerant compositionsof the present invention comprise compounds with 2 to 12 carbon atoms.In another embodiment the fluoroolefins comprise compounds with 3 to 10carbon atoms, and in yet another embodiment the fluoroolefins comprisecompounds with 3 to 7 carbon atoms. Representative fluoroolefins includebut are not limited to all compounds as listed in Table 1, Table 2, andTable 3.

One embodiment of the present invention provides fluoroolefins havingthe formula E- or Z—R¹CH═CHR² (Formula I), wherein R¹ and R² are,independently, C₁ to C₆ perfluoroalkyl groups. Examples of R¹ and R²groups include, but are not limited to, OCF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂,CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃, CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃,CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, andC(CF₃)₂CF₂C₂F₅. In one embodiment the fluoroolefins of Formula I have atleast about 4 carbon atoms in the molecule. In another embodiment, thefluoroolefins of Formula I have at least about 5 carbon atoms in themolecule. Exemplary, non-limiting Formula I compounds are presented inTable 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluorobut-2-ene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E CF₃CH═CHCF₂C₂F₅1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF₃CH═CHCF(CF₃)₂1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14ECF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iECF₃CH═CHCF₂CF—(CF₃)₂1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyhex-2-ene F14sECF₃CH═CHCF(CF₃)—C₂F₅1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene F14tECF₃CH═CHC(CF₃)₃1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23EC₂F₅CH═CHCF₂C₂F₅ 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iEC₂F₅CH═CHCF(CF₃)₂1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyhex-3-ene F15ECF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-eneF15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene F15tE CF₃CH═CH—C(CF₃)₂C₂F₅1,1,1,5,5,6,6,6-octafluoro-4,4- bis(trifluoromethyl)hex-2-ene F24EC₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-eneF24iE C₂F₅CH═CHCF₂CF—(CF₃)₂ 1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene F24sE C₂F₅CH═CHCF(CF₃)—C₂F₅1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5- (trifluoromethyl)hept-3-ene F24tEC₂F₅CH═CHC(CF₃)₃ 1,1,1,2,2,6,6,6-octafluoro-5,5-enebis(trifluoromethyl)hex-3-ene F33E C₂F₅CF₂CH═CH—CF₂C₂F₅1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE(CF₃)₂CFCH═CH—CF(CF₃)₂ 1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-ene F33iE C₂F₅CF₂CH═CH—CF(CF₃)₂1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2- (trifluoromethyl)hept-3-ene F16ECF₃CH═CH(CF₂)₅CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-ene F16sE CF₃CH═CHCF(CF₃)(CF₂)₂C₂F₅1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4- (trifluoromethyl)hept-2-eneF16tE CF₃CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene F25EC₂F₅CH═CH(CF₂)₄CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iEC₂F₅CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-ene F25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,6,6,7,7,7-decafluoro-5,5- bis(trifluoromethyl)hept-3-ene F34EC₂F₅CF₂CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F34iEC₂F₅CF₂CH═CH—CF₂CF(CF₃)₂ 1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-ene F34sE C₂F₅CF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6- (trifluoromethyl)oct-4-eneF34tE C₂F₅CF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyhhept-3-ene F3i4E (CF₃)₂CFCH═CH—(CF₂)₃CF₃1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)oct-3-ene2(trifluoromethyl)oct-3-ene F3i4iE (CF₃)₂CFCH═CH—CF₂CF(CF₃)₂1,1,1,2,5,5,6,7,7,7-decafluoro-2,6- bis(trifluoromethyhhept-3-ene F3i4sE(CF₃)₂CFCH═CH—CF(CF₃)C₂F₅ 1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)hept-3-ene F3i4tE (CF₃)₂CFCH═CH—C(CF₃)₃1,1,1,2,6,6,6-heptafluoro-2,5,5- tris(trifluoromethyl)hex-3-ene F26EC₂F₅CH═CH(CF₂)₅CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-3-ene F26sE C₂F₅CH═CHCF(CF₃)(CF₂)₂C₂F₅1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene F26tE C₂F₅CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5- bis(trifluoromethyl)oct-3-eneF35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃ 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene F35iE C₂F₅CF₂CH═CH—1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8- CF₂CF₂CF(CF₃)₂(trifluoromethyl)non-4-ene F35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6- bis(trifluoromethyl)oct-4-eneF3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene F3i5iE (CF₃)₂CFCH═CH—1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7- CF₂CF₂CF(CF₃)₂bis(trifluoromethyl)oct-3-ene F3i5tE (CF₃)₂CFCH═CH—C(CF₃)₂C₂F₅1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene F44ECF₃(CF₂)₃CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec-5-ene F441ECF₃(CF₂)₃CH═CH— 1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-CF₂CF(CF₃)₂ (trifluoromethyl)non-4-ene F44sE CF₃(CF₂)₃CH═CH—1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3- CF(CF₃)C₂F₅(trifluoromethyl)non-4-ene F44tE CF₃(CF₂)₃CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2- bis(trifluoromethyl)oct-3-eneF4i4iE (CF₃)₂CFCF₂CH═CH— 1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-CF₂CF(CF₃)₂ bis(trifluoromethyl)oct-4-ene F4i4sE (CF₃)₂CFCF₂CH═CH—1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6- CF(CF₃)C₂F₅bis(trifluoromethyl)oct-4-ene F4i4tE (CF₃)₂CFCF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,7,7,7-nonafluoro-2,2,5- F4s4sE C₂F₅CF(CF₃)CH═CH—1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6- CF(CF₃)C₂F₅tris(trifluoromethyl)hept-3-ene F4s4tE C₂F₅CF(CF₃)CH═CH—C(CF₃)₃1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5- tris(trifluoromethyl)hept-3-eneF4t4tE (CF₃)₃CCH═CH—C(CF₃)₃ 1,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyliodide of the formula R¹ with a perfluoroalkyltrihydroolefin of theformula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formulaR¹CH₂CHIR². This trihydroiodoperfluoroalkane can then bedehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR²may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane ofthe formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyliodide of the formula R²I with a perfluoroalkyltrihydroolefin of theformula R¹CH═CH₂.

Said contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include fabricated from stainlesssteels, in particular of the austenitic type, and the well-known highnickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickelbased alloys and Inconel® nickel-chromium alloys.

Alternatively, the reaction may take be conducted in semi-batch mode inwhich the perfluoroalkyltrihydroolefin reactant is added to theperfluoroalkyl iodide reactant by means of a suitable addition apparatussuch as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefinshould be between about 1:1 to about 4:1, preferably from about 1.5:1 to2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1adduct as reported by Jeanneaux, et. al. in Journal of FluorineChemistry, Vol. 4, pages 261-270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide withsaid perfluoroalkyltrihydroolefin are preferably within the range ofabout 150° C. to 300° C., preferably from about 170° C. to about 250°C., and most preferably from about 180° C. to about 230° C. Suitablecontact times for the reaction of the perfluoroalkyl iodide with theperfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours,preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be useddirectly in the dehydroiodination step or may preferably be recoveredand purified by distillation prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting thetrihydroiodoperfluoroalkane with a basic substance. Suitable basicsubstances include alkali metal hydroxides (e.g., sodium hydroxide orpotassium hydroxide), alkali metal oxide (for example, sodium oxide),alkaline earth metal hydroxides (e.g., calcium hydroxide), alkalineearth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g.,sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, ormixtures of basic substances such as soda lime. Preferred basicsubstances are sodium hydroxide and potassium hydroxide. Said contactingof the trihydroiodoperfluoroalkane with a basic substance may take placein the liquid phase preferably in the presence of a solvent capable ofdissolving at least a portion of both reactants. Solvents suitable forthe dehydroiodination step include one or more polar organic solventssuch as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol,n-butanol, isobutanol, and tertiary butanol), nitriles (e.g.,acetonitrile, propionitrile, butyronitrile, benzonitrile, oradiponitrile), dimethyl sulfoxide, N,N-dimethylformamide,N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend onthe boiling point product and the ease of separation of traces of thesolvent from the product during purification. Typically, ethanol orisopropanol are good solvents for the reaction.

Typically, the dehydroiodination reaction may be carried out by additionof one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction may be fabricated from glass, ceramic, ormetal and is preferably agitated with an impeller or stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about10° C. to about 100° C., preferably from about 20° C. to about 70° C.The dehydroiodination reaction may be carried out at ambient pressure orat reduced or elevated pressure. Of note are dehydroiodination reactionsin which the compound of Formula I is distilled out of the reactionvessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted bycontacting an aqueous solution of said basic substance with a solutionof the trihydroiodoperfluoroalkane in one or more organic solvents oflower polarity such as an alkane (e.g., hexane, heptane, or octane),aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g.,methylene chloride, chloroform, carbon tetrachloride, orperchloroethylene), or ether (e.g., diethyl ether, methyl tert-butylether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane,dimethoxyethane, diglyme, or tetraglyme) in the presence of a phasetransfer catalyst. Suitable phase transfer catalysts include quaternaryammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammoniumhydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammoniumchloride, and tricaprylylmethylammonium chloride), quaternaryphosphonium halides (e.g., triphenylmethylphosphonium bromide andtetraphenylphosphonium chloride), or cyclic polyether compounds known inthe art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in theabsence of solvent by adding the trihydroiodoperfluoroalkane to a solidor liquid basic substance.

Suitable reaction times for the dehydroiodination reactions are fromabout 15 minutes to about six hours or more depending on the solubilityof the reactants. Typically the dehydroiodination reaction is rapid andrequires about 30 minutes to about three hours for completion.

The compound of Formula I may be recovered from the dehydroiodinationreaction mixture by phase separation after addition of water, bydistillation, or by a combination thereof.

In another embodiment of the present invention, fluoroolefins comprisecyclic fluoroolefins (cyclo-[CX═CY(CZW)_(n)—] (Formula II) wherein X, Y,Z, and W are independently selected from H and F, and n is an integerfrom 2 to 5). In one embodiment the fluoroolefins of Formula II, have atleast about 3 carbon atoms in the molecule. In another embodiment, thefluoroolefins of Formula II have at least about 4 carbon atoms in themolecule. In yet another embodiment, the fluoroolefins of Formula IIhave at least about 5 carbon atoms in the molecule. Representativecyclic fluoroolefins of Formula II are listed in Table 2.

TABLE 2 Cyclic fluoroolefins Structure Chemical name FC-C1316cccyclo-CF₂CF₂CF═CF— 1,2,3,3,4,4- hexafluorocyclobutene HFC-C1334cccyclo-CF₂CF₂CH═CH— 3,3,4,4-tetrafluorocyclobutene HFC-C1436cyclo-CF₂CF₂CF₂CH═CH— 3,3,4,4,5,5,- hexafluorocyclopentene FC-C1418ycyclo-CF₂CF═CFCF₂CF₂— 1,2,3,3,4,4,5,5- octafluorocyclopenteneFC-C151-10y cyclo-CF₂CF═CFCF₂CF₂CF₂— 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene

The refrigerant compositions of the present invention may comprise asingle compound of Formula I or Formula II, for example, one of thecompounds in Table 1 or Table 2, or may comprise a combination ofcompounds of Formula I or Formula II.

In another embodiment, fluoroolefins may comprise those compounds listedin Table 3.

TABLE 3 Name Structure Chemical name HFO-1225ye CF₃CF═CHF1,2,3,3,3-pentafluoro-1-propene HFO-1225zc CF₃CH═CF₂1,1,3,3,3-pentafluoro-1-propene HFO-1225yc CHF₂CF═CF₂1,1,2,3,3-pentafluoro-1-propene HFO-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFO-1234yf CF₃CF═CH₂2,3,3,3-tetrafluoro-1-propene HFO-1234ze CF₃CH═CHF1,3,3,3-tetrafluoro-1-propene HFO-1234yc CH₂FCF═CF₂1,1,2,3-tetrafluoro-1-propene HFO-1234zc CHF₂CH═CF₂1,1,3,3-tetrafluoro-1-propene HFO-1243yf CHF₂CF═CH₂2,3,3-trifluoro-1-propene HFO-1243zf CF₃CH═CH₂ 3,3,3-trifluoro-1-propeneHFO-1243yc CH₃CF═CF₂ 1,1,2-trifluoro-1-propene HFO-1243zc CH₂FCH═CF₂1,1,3-trifluoro-1-propene HFO-1243ye CH₂FCF═CHF1,2,3-trifluoro-1-propene HFO-1243ze CHF₂CH═CHF1,3,3-trifluoro-1-propene FC-1318my CF₃CF═CFCF₃1,1,1,2,3,4,4,4-octafluoro-2- butene FC-1318cy CF₃CF₂CF═CF₂1,1,2,3,3,4,4,4-octafluoro-1- butene HFO-1327my CF₃CF═CHCF₃1,1,1,2,4,4,4-heptafluoro-2-butene HFO-1327ye CHF═CFCF₂CF₃1,2,3,3,4,4,4-heptafluoro-1-butene HFO-1327py CHF₂CF═CFCF₃1,1,1,2,3,4,4-heptafluoro-2-butene HFO-1327et (CF₃)₂C═CHF 1,3,3,3-tetrafluoro-2- (trifluoromethyl)-1-propene HFO-1327cz CF₂═CHCF₂CF₃1,1,3,3,4,4,4-heptafluoro-1-butene HFO-1327cye CF₂═CFCHFCF₃1,1,2,3,4,4,4-heptafluoro-1-butene HFO-1327cyc CF₂═CFCF₂CHF₂1,1,2,3,3,4,4-heptafluoro-1-butene HFO-1336yf CF₃CF₂CF═CH₂2,3,3,4,4,4-hexafluoro-1-butene HFO-1336ze CHF═CHCF₂CF₃ 1,3,3,4,4,4-hexafluoro-1-butene HFO-1336eye CHF═CFCHFCF₃ 1,2,3,4,4,4-hexafluoro-1-butene HFO-1336eyc CHF═CFCF₂CHF₂ 1,2,3,3,4,4-hexafluoro-1-butene HFO-1336pyy CHF₂CF═CFCHF₂ 1,1,2,3,4,4-hexafluoro-2-but ne HFO-1336qy CH₂FCF═CFCF₃ 1,1,1,2,3,4-hexafluoro-2-butene HFO-1336pz CHF₂CH═CFCF₃ 1,1,1,2,4,4-hexafluoro-2-butene HFO-1336mzy CF₃CH═CFCHF₂ 1,1,1,3,4,4-hexafluoro-2-butene HFO-1336qc CF₂═CFCF₂CH₂F1,1,2,3,3,4-hexafluoro-1-butene HFO-1336pe CF₂═CFCHFCHF₂1,1,2,3,4,4-hexafluoro-1-butene HFO-1336ft CH₂═C(CF₃)₂3,3,3-trifluoro-2-(trifluoromethyl)-1- propene HFO-1345qz CH₂FCH═CFCF₃1,1,1,2,4-pentafluoro-2-butene HFO-1345mzy CF₃CH═CFCH₂F1,1,1,3,4-pentafluoro-2-butene HFO-1345fz CF₃CF₂CH═CH₂3,3,4,4,4-pentafluoro-1-butene HFO-1345mzz CHF₂CH═CHCF₃1,1,1,4,4-pentafluoro-2-butene HFO-1345sy CH₃CF═CFCF₃1,1,1,2,3-pentafluoro-2-butene HFO-1345fyc CH₂═CFCF₂CHF₂2,3,3,4,4-pentafluoro-1-butene HFO-1345pyz CHF2CF═CHCHF₂1,1,2,4,4-pentafluoro-2-butene HFO-1345cyc CH₃CF₂CF═CF₂1,1,2,3,3-pentafluoro-1-butene HFO-1345pyy CH₂FCF═CFCHF₂1,1,2,3,4-pentafluoro-2-butene HFO-1345eyc CH₂FCF₂CF═CF₂1,2,3,3,4-pentafluoro-1-butene HFO-1345ctm CF₂═C(CF₃)(CH₃)1,1,3,3,3-pentafluoro-2-methy1-1- propene HFO-1345ftp CH₂═C(CHF₂)(CF₃)2-(difluoromethyl)-3,3,3-trifluoro-1- propene HFO1345fye CH₂═CFCHFCF₃2,3,4,4,4-pentafluoro-1-butene HFO-1345eyf CHF═CFCH₂CF₃1,2,4,4,4-pentafluoro-1-butene HFO-1345eze CHF═CHCHFCF₃1,3,4,4,4-pentafluoro-1-butene HFO-1345ezc CHF═CHCF₂CHF₂1,3,3,4,4-pentafluoro-1-butene HFO-1345eye CHF═CFCHFCHF₂1,2,3,4,4-pentafluoro-1-butene HFO-1354fzc CH₂═CHCF₂CHF₂3,3,4,4-tetrafluoro-1-butene HFO-1354ctp CF₂═C(CHF₂)(CH₃)1,1,3,3-tetrafluoro-2-methy1-1- propene HFO-1354etm CHF═C(CF₃)(CH₃)1,3,3,3-tetrafluoro-2-methy1-1- propene HFO-1354tfp CH₂═C(CHF₂)₂2-(difluoromethyl)-3,3-difluoro-1- propene HFO-1354my CF₃CF═CHCH₃1,1,1,2-tetrafluoro-2-butene HFO-1354mzy CH3CF═CHCF₃1,1,1,3-tetrafluoro-2-butene FC-141-10myy CF₃CF═CFCF₂CF₃1,1,1,2,3,4,4,5,5,5-decafluoro-2- pentene FC-141-10cy CF₂═CFCF₂CF₂CF₃1,1,2,3,3,4,4,5,5,5-decafluoro-1- pentene HFO-1429mzt (CF₃)₂C═CHCF₃1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene HFO-1429myzCF₃CF═CHCF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-2- pentene HFO-1429mzyCF₃CH═CFCF₂CF₃ 1,1,1,3,4,4,5,5,5-nonafluoro-2- pentene HFO-1429eycCHF═CFCF₂CF₂CF₃ 1,2,3,3,4,4,5,5,5-nonafluoro-1- pentene HFO-1429czcCF₂═CHCF₂CF₂CF₃ 1,1,3,3,4,4,5,5,5-nonafluoro-1- pentene HFO-1429cyccCF₂═CFCF₂CF₂CHF₂ 1,1,2,3,3,4,4,5,5-nonafluoro-1- pentene HFO-1429pyyCHF₂CF═CFCF₂CF₃ 1,1,2,3,4,4,5,5,5-nonafluoro-2- pentene HFO-1429myycCF₃CF═CFCF₂CHF₂ 1,1,1,2,3,4,4,5,5-nonafluoro-2- pentene HFO-1429myyeCF₃CF═CFCHFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-2- pentene HFO-1429eyymCHF═CFCF(CF₃)₂ 1,2,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-buteneHFO-1429cyzm CF₂═CFCH(CF₃)₂ 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene HFO-1429mzt CF₃CH═C(CF₃)₂1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene HFO-1429czymCF₂═CHCF(CF₃)₂ 1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-buteneHFO-1438fy CH₂═CFCF₂CF₂CF₃ 2,3,3,4,4,5,5,5-octafluoro-1- penteneHFO-1438eycc CHF═CFCF₂CF₂CHF₂ 1,2,3,3,4,4,5,5-octafluoro-1- penteneHFO-1438ftmc CH₂═C(CF₃)CF₂CF₃ 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFO-1438czzm CF₂═CHCH(CF₃)₂1,1,4,4,4-pentafluoro-3- (trifluoromethyl)-1-butene HFO-1438ezymCHF═CHCF(CF₃)₂ 1,3,4,4,4-pentafluoro-3- (trifluoromethyl)-1-buteneHFO-1438ctmf CF₂═C(CF₃)CH₂CF₃ 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFO-1447fzy (CF₃)₂CFCH═CH₂3,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFO-1447fzCF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1- pentene HFO-1447fyccCH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1- pentene HFO-1447czcfCF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1- pentene HFO-1447mytmCF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3- methyl-2-buteneHFO-1447fyz CH₂═CFCH(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene HFO-1447ezz CHF═CHCH(CF₃)₂1,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFO-1447qztCH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-2- (trifluoromethyl)-2-buteneHFO-1447syt CH₃CF═C(CF₃)₂ 2,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-butene HFO-1456szt (CF₃)₂C═CHCH₃3-(trifluoromethyl)-4,4,4-trifluoro-2- butene HFO-1456szy CF₃CF₂CF═CHCH₃3,4,4,5,5,5-hexafluoro-2-pentene HFO-1456mstz CF₃C(CH₃)═CHCF₃1,1,1,4,4,4-hexafluoro-2-methy1-2- butene HFO-1456fzce CH₂═CHCF₂CHFCF₃3,3,4,5,5,5-hexafluoro-1-pentene HFO-1456ftmf CH₂═C(CF₃)CH₂CF₃4,4,4-trifluoro-2-(trifluoromethyl)-1- butene FC-151-12c CF₃(CF₂)₃CF═CF₂1,1,2,3,3,4,4,5,5,6,6,6- dodecafluoro-1-hexene (or perfluoro-1-hexene)FC-151-12mcy CF₃CF₂CF═CFCF₂CF₃ 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (or perfluoro-3-hexene) FC-151-12mmtt(CF₃)₂C═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene FC-151-12mmzz (CF₃)₂CFCF═CFCF₃1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl)-2-penteneHFO-152-11mmtz (CF₃)₂C═CHC₂F₅ 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene HFO-152-11mmyyz (CF₃)₂CFCF═CHCF₃1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)-2-pentene PFBECF₃CF₂CF₂CF₂CH═CH₂ 3,3,4,4,5,5,6,6,6-nonafluoro-1- (or HFO-1549fz)hexene (or perfluorobutylethylene) HFO-1549fztmm CH₂═CHC(CF₃)₃4,4,4-trifluoro-3,3- bis(trifluoromethyl)-1-butene HFO-1549mmtts(CF₃)₂C═C(CH₃)(CF₃) 1,1,1,4,4,4-hexafluoro-3-methy1-2-(trifluoromethyl)-2-butene HFO-1549fycz CH₂═CFCF₂CH(CF₃)₂2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl)-1-pentene HFO-1549mytsCF₃CF═C(CH₃)CF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-3- methy1-2-penteneHFO-1549mzzz CF₃CH═CHCH(CF₃)₂ 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene HFO-1558szy CF₃CF₂CF₂CF═CHCH₃3,4,4,5,5,6,6,6-octafluoro-2- hexene HFO-1558fzccc CH₂═CHCF₂CF₂CF₂CHF₂3,3,4,4,5,5,6,6-octafluoro-2- hexene HFO-1558mmtzc (CF₃)₂C═CHCF₂CH₃1,1,1,4,4-pentafluoro-2- (trifluoromethyl)-2-pentene HFO-1558ftmfCH₂═C(CF₃)CH₂C₂F₅ 4,4,5,5,5-pentafluoro-2- (trifluoromethyl)-1-penteneHFO-1567fts CF₃CF₂CF₂C(CH₃)═CH₂ 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene HFO-1567szz CF₃CF₂CF₂CH═CHCH₃4,4,5,5,6,6,6-heptafluoro-2- hexene HFO-1567fzfc CH₂═CHCH₂CF₂C₂F₅4,4,5,5,6,6,6-heptafluoro-1- hexene HFO-1567sfyy CF₃CF₂CF═CFC₂H₅1,1,1,2,2,3,4-heptafluoro-3- hexene HFO-1567fzfy CH₂═CHCH₂CF(CF₃)₂4,5,5,5-tetrafluoro-4- (trifluoromethyl)-1-pentene HFO-1567myzzmCF₃CF═CHCH(CF₃)(CH₃) 1,1,1,2,5,5,5-heptafluoro-4- methy1-2-penteneHFO-1567mmtyf (CF₃)₂C═CFC₂H₅ 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene FC-161-14myy CF₃CF═CFCF₂CF₂C₂F₅1,1,1,2,3,4,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene FC-161-14mcyyCF₃CF₂CF═CFCF₂C₂F₅ 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene HFO-162-13mzy CF₃CH═CFCF₂CF₂C₂F₅1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene HFO162-13myzCF₃CF═CHCF₂CF₂C₂F₅ 1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-hepteneHFO-162-13mczy CF₃CF₂CH═CFCF₂C₂F₅ 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene HFO-162-13mcyz CF₃CF₂CF═CHCF₂C₂F₅1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene PEVE CF₂═CFOCF₂CF₃pentafluoroethyl trifluorovinyl ether PMVE CF₂═CFOCF₃ trifluoromethyltrifluorovinyl ether

The compounds listed in Table 2 and Table 3 are available commerciallyor may be prepared by processes known in the art or as described herein.1,1,1,4,4-pentafluoro-2-butene may be prepared from1,1,1,2,4,4-hexafluorobutane (CHF₂CH₂CHFCF₃) by dehydrofluorination oversolid KOH in the vapor phase at room temperature. The synthesis of1,1,1,2,4,4-hexafluorobutane is described in U.S. Pat. No. 6,066,768,incorporated herein by reference. 1,1,1,4,4,4-hexafluoro-2-butene may beprepared from 1,1,1,4,4,4-hexafluoro-2-iodobutane (CF₃CHICH₂F₃) byreaction with KOH using a phase transfer catalyst at about 60° C. Thesynthesis of 1,1,1,1,4,4,-hexafluoro-2-iodobutane may be carried out byreaction of perfluoromethyl iodide (F₃I) and 3,3,3-trifluoropropene(CF₃CH═H₂) at about 200° C. under autogenous pressure for about 8 hours.

3,4,4,5,5,5-hexafluoro-2-pentene may be prepared by dehydrofluorinationof 1,1,1,2,2,3,3-heptafluoropentane (CF₃CF₂CF₂CH₂CH₃) using solid KOH orover a carbon catalyst at 200-300° C. 1,1,1,2,2,3,3-heptafluoropentanemay be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene(CF₃CF₂CF₂CH═CH₂).

1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,3,3,4-heptafluorobutane (CH₂FCF₂CHFCF₃) using solid KOH.

1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,2,4,4-heptafluorobutane (CHF₂CH₂CF₂CF₃) using solid KOH.

1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4,4-heptafluorobutane (CF₃CH₂CF₂CHF₂) using solid KOH.

1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,2,2,3-hexafluorobutane (CH₂FCH₂CF₂CF₃) using solid KOH.

1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4-hexafluorobutane (CF₃CH₂CF₂CH₂F) using solid KOH.

1,1,1,3-tetrafluoro-2-butene may be prepared by reacting1,1,1,3,3-pentafluorobutane (CF₃CH₂CF₂CH₃) with aqueous KOH at 120° C.

1,1,1,4,4,5,5,5-octafluoro-2-pentene may be prepared from(CF₃CHICH₂CF₂CF₃) by reaction with KOH using a phase transfer catalystat about 60° C. The synthesis of4-iodo-1,1,1,2,2,5,5,5-octafluoropentane may be carried out by reactionof perfluoroethyliodide (CF₃CF₂I) and 3,3,3-trifluoropropene at about200° C. under autogenous pressure for about 8 hours.

1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF₃CF₂CHICH₂CF₂CF₃) byreaction with KOH using a phase transfer catalyst at about 60° C. Thesynthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane may be carriedout by reaction of perfluoroethyliodide (CF₃CF₂I) and3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂) at about 200° C. underautogenous pressure for about 8 hours.

1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene may be preparedby the dehydrofluorination of1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane(CF₃CHICH₂CF(CF₃)₂) with KOH in isopropanol. CF₃CHICH₂CF(CF₃)₂ is madefrom reaction of (CF₃)₂CFI with CF₃CH═CH₂ at high temperature, such asabout 200° C.

1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene may be prepared by the reactionof 1,1,1,4,4,4-hexafluoro-2-butene (CF₃CH═CHCF₃) withtetrafluoroethylene (CF₂═CF₂) and antimony pentafluoride (SbF₅).

2,3,3,4,4-pentafluoro-1-butene may be prepared by dehydrofluorination of1,1,2,2,3,3-hexafluorobutane over fluorided alumina at elevatedtemperature.

2,3,3,4,4,5,5,5-ocatafluoro-1-pentene may be prepared bydehydroflurination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solidKOH.

1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane overfluorided alumina at elevated temperature.

2,3,3,3-tetrafluoro-1-propene may be prepared by converting at least oneof HCFC-244bb or HFC-245eb into HFO-1234yf.

1,3,3,3-tetrafluoro-1-propene may be prepared by HFC-245fa intoHFO-1234ze.

Many of the compounds of Formula I, Formula II, Table 1, Table 2, andTable 3 exist as different configurational isomers or stereoisomers.When the specific isomer is not designated, the present invention isintended to include all single configurational isomers, singlestereoisomers, or any combination thereof. For instance, F11E is meantto represent the E-isomer, Z-isomer, or any combination or mixture ofboth isomers in any ratio. As another example, HFO-1225ye is meant torepresent the E-isomer, Z-isomer, or any combination or mixture of bothisomers in any ratio.

In one particular embodiment, the fluoroolefin component of theinventive composition comprises HFO-1234yf and/or HFO-1234ze. In anotherparticular embodiment, the fluorolefin comprises HFO-1234yf and/orHFO-1234ze having a purity of greater than 99 wt %, greater than 99.5 wt% pure and in some cases greater than 99.5 to 99, 98 percent pure. Inanother particular embodiment, the fluoroleffin comprises at least 99.5wt % of 1234yf or 1234ze and less than 0.5 and greater than 0.0001 wt %of the other fluorolefin, less than 0.3 and in some cases less than 0.2.

In another particular embodiment, the fluoroolefin component cancomprise the refrigerant compositions disclosed in U.S. Pat. Nos.8,147,709 and 8,877,086; hereby incorporated by reference.

In another particular embodiment, the fluoroolefin component comprisesgreater than about 99.5 wt % HFO-1234yf and one or more members selectedfrom the group consisting of HFO-1225ye, HFO-1243zf, HFO-1234ze,HFC-236ea, HFC-244bb, HFC-245fa, HFC-245eb, HFC-245cb,3,3,3-trifluoropropyne, and mixtures thereof. The amount of HFO-1225ye(E/Z isomers) can range from greater than 0 to about 200 ppm by weight,about 1 to about 150 ppm and in some cases about 5 to about 50 ppm. Theamount of HFO1243zf can range from about 0.1 to about 250 ppm, about 10to about 200 ppm and in some cases about 15 to about 150 ppm. The amountof HFO-1234ze (E isomer) can range from about 1 to about 1,500 ppm,about 5 to about 1,000 ppm and in some cases about 50 to 500 ppm. Theamount of HFC-236ea can range from about 1 to about 50 ppm, about 5 toabout 25 and in some cases about 10 to about 20 ppm. The amount ofHFC-245fa, HFC-245eb and/or HFC-245cb can range from about 0 to about20, about 1 to about 15 and in some cases about 5 to about 10 ppm. Theamount of 3,3,3-trifluoropropyne can range from about 0 to about 500ppm, about 1 to about 300 ppm and in some cases about 5 to about 100ppm.

In another embodiment, the fluorolefin component comprises HFO-1234yfand at least one additional compound selected from the group consistingof 1114, 1123, 1131a, 1131trans, 1140, 1214ya, 1216, 1224yd, 1225ye(E),1233zd(E), 1234ze(E), 1252, 143a, 225, 245eb, 254eb, 263fb, CF3CF2I,236fa, 142b, 244cc, 1223, 1132a, 2316, 1327 isomer, 1336mzzE, 1336isomer, 1234zeZ and 1224 isomer. In one particular embodiment, thefluorolefin component comprises HFO-1234yf and greater than zero andless than about 1 wt %, less than about 0.5 wt % and in some cases lessthan 0.25 wt % of additional compounds. In a further embodiment, theinventive inhibitor can used with at least one of HCFO-1233zd andHCFO-1224yd, and refrigerant compositions of blends comprising at leastone of HCFO-1233zd and HCFO-1224yd.

Any suitable effective amount of inhibitor may be used in the foregoingrefrigerant compositions comprising at least one fluoroolefin. Asdescribed herein, the phrase “effective amount” refers to an amount ofinhibitor of the present invention which, when added to a compositioncomprising at least one fluoroolefin, results in a composition whereinthe fluoroolefin will not interact with an initiator, and/or degrade toproduce as great a reduction in performance, for example, when in use ina cooling apparatus as compared to the composition without an inhibitorand be present in a liquid phase fluoroolefin as well as a lubricant.For cooling apparatus, such effective amounts of inhibitor may bedetermined by way of testing under the conditions of standard testASHRAE 97-2007 (RA 2017) In a certain embodiment of the presentinvention, an effective amount may be said to be that amount ofinhibitor that when included as a component of a refrigerant compositioncomprising at least one fluoroolefin and a lubricant allows a coolingapparatus utilizing said composition comprising at least onefluoroolefin to perform at the same level of refrigeration performanceand cooling capacity as if a composition comprising1,1,1,2-tetrafluoroethane (R-134a), or other standard refrigerant (R-12,R-22, R-502, R-507A, R-508, R401A, R401B, R402A, R402B, R408, R-410A,R-404A, R407C, R-413A, R-417A, R-422A, R-422B, R-422C, R-422D, R-423,R-114, R-11, R-113, R-123, R-124, R236fa, or R-245fa) depending uponwhat refrigerant may have been used in a similar system in the past,were being utilized as the working fluid.

The instant invention employs effective amounts of at least one of theforegoing inhibitors. While any suitable effective amount can beemployed, effective amounts comprise from about 0.001 wt % to about 10wt %, about 0.01 wt % to about 5 wt %, about 0.3 wt % to about 4 wt %,about 0.3 wt % to about 1 wt % based on the total weight of refrigerantcompositions comprising at least one fluoroolefin containing refrigerantcompositions as described herein. In one embodiment, an effective amountcomprises about 10 to about 2,000 ppm by weight, about 10 to about 1,000ppm and in some cases about 10 to about 500 ppm of at least oneinitiator.

In one embodiment of the invention, the inhibitor partitions between thetwo liquid phases, namely, the liquid phase fluoroolefin and thelubricant. The amount of inhibitor present in the liquid phase of thefluoroolefin can range about 10 to about 80 wt %, about 25 to about 75wt % and, in some cases, about 45 to about 60 wt % of the inhibitor withthe remainder of the inhibitor predominantly present in the lubricantphase.

One embodiment of the invention relates to any of the foregoingrefrigerant compositions and further comprising at least oneanti-oxidant. While any suitable oxidant can be employed, examples ofsuitable oxidants comprise at least one member selected from the groupconsisting of butylated hydroxytoluene, butylated hydroxyanisole,tertiary-butylhydroquinone, gallate, 2-phenyl-2-propanol,1-(2,4,5-trihydroxyphenyl)-1-butanone, phenolics, bisphenol methanederivatives, 2,2′-methylene bis (4-methyl-6-t-butyl phenol), andcombinations thereof. The amount of anti-oxidant can range from about0.01 to about 5,000 ppm by weight, about 0.03 to about 2000 ppm and insome cases about 0.05 to about 1000 ppm. An example of one particularembodiment relates to using the foregoing anti-oxidant with at least oneinhibitor comprising α-terpinene and limonene. An example of oneparticular embodiment relates to using the foregoing anti-oxidant withan inhibitor comprising at least one of α-terpinene and limonene.

In one embodiment, the foregoing refrigerant compositions of the presentinvention may further comprise at least one additional compound selectedfrom the group consisting of fluoroolefins (as described previouslyherein), hydrofluorocarbons, hydrocarbons, dimethyl ether, CF₃I,ammonia, carbon dioxide (CO₂) and mixtures thereof, meaning mixtures ofany of the additional compounds listed in this paragraph. The amount ofthe additional compound can range from about 1 to about 90% by weight,about 5 to about 75% and in some cases about 10 to about 50%.

In one embodiment, the additional compounds comprise hydrofluorocarbons.

The hydrofluorocarbon (HFC) compounds of the present invention comprisesaturated compounds containing carbon, hydrogen, and fluorine. Ofparticular utility are hydrofluorocarbons having 1-7 carbon atoms andhaving a normal boiling point of from about −90° C. to about 80° C.Hydrofluorocarbons are commercial products available from a number ofsources, or may be prepared by methods known in the art. Representativehydrofluorocarbon compounds include but are not limited to fluoromethane(CH₃F, HFC-41), difluoromethane (CH₂F₂, HFC-32), trifluoromethane (CHF₃,HFC-23), pentafluoroethane (CF₃CHF₂, HFC-125), 1,1,2,2-tetrafluoroethane(CHF₂CHF₂, HFC-134), 1,1,1,2-tetrafluoroethane (CF₃CH₂F, HFC-134a),1,1,1-trifluoroethane (CF₃CH₃, HFC-143a), 1,1-difluoroethane (CHF₂CH₃,HFC-152a), fluoroethane (CH₃CH₂F, HFC-161),1,1,1,2,2,3,3-heptafluoropropane (CF₃CF₂CHF₂, HFC-227ca),1,1,1,2,3,3,3-heptafluoropropane (CF₃CHFCF₃, HFC-227ea),1,1,2,2,3,3,-hexafluoropropane (CHF₂CF₂CHF₂, HFC-236ca),1,1,1,2,2,3-hexafluoropropane (CF₃CF₃CH₂F, HFC-236cb),1,1,1,2,3,3-hexafluoropropane (CF₃CHFCHF₂, HFC-236ea),1,1,1,3,3,3-hexafluoropropane (CF₃CH₂CF₃, HFC-236fa),1,1,2,2,3-pentafluoropropane (CHF₂CF₂CH₂F, HFC-245ca),1,1,1,2,2-pentafluoropropane (CF₃CF₂CH₃, HFC-245cb),1,1,2,3,3-pentafluoropropane (CHF₂CHFCHF₂, HFC-245ea),1,1,1,2,3-pentafluoropropane (CF₃CHFCH₂F, HFC-245eb),1,1,1,3,3-pentafluoropropane (CF₃CH₂CHF₂, HFC-245fa),1,2,2,3-tetrafluoropropane (CH₂FCF₂CH₂F, HFC-254ca),1,1,2,2-tetrafluoropropane (CHF₂CF₂CH₃, HFC-254cb),1,1,2,3-tetrafluoropropane (CHF₂CHFCH₂F, HFC-254ea),1,1,1,2-tetrafluoropropane (CF₃CHFCH₃, HFC-254eb),1,1,3,3-tetrafluoropropane (CHF₂CH₂CHF₂, HFC-254fa),1,1,1,3-tetrafluoropropane (CF₃CH₂CH₂F, HFC-254fb),1,1,1-trifluoropropane (CF₃CH₂CH₃, HFC-263fb), 2,2-difluoropropane(CH₃CF₂CH₃, HFC-272ca), 1,2-difluoropropane (CH₂FCHFCH₃, HFC-272ea),1,3-difluoropropane (CH₂FCH₂CH₂F, HFC-272fa), 1,1-difluoropropane(CHF₂CH₂CH₃, HFC-272fb), 2-fluoropropane (CH₃CHFCH₃, HFC-281ea),1-fluoropropane (CH₂FCH₂CH₃, HFC-281fa),1,1,2,2,3,3,4,4-octafluorobutane (CHF₂CF₂CF₂CHF₂, HFC-338pcc),1,1,1,2,2,4,4,4-octafluorobutane (CF₃CH₂CF₂CF₃, HFC-338mf),1,1,1,3,3-pentafluorobutane (CF₃CH₂CHF₂, HFC-365mfc),1,1,1,2,3,4,4,5,5,5-decafluoropentane (CF₃CHFCHFCF₂CF₃, HFC-43-10mee),and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane(CF₃CF₂CHFCHFCF₂CF₂CF₃, HFC-63-14mee).

In another embodiment, the additional compounds comprise hydrocarbons.The hydrocarbons of the present invention comprise compounds having onlycarbon and hydrogen. Of particular utility are compounds having 3-7carbon atoms. Hydrocarbons are commercially available through numerouschemical suppliers. Representative hydrocarbons include but are notlimited to propane, n-butane, isobutane, cyclobutane, n-pentane,2-methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane,2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane,3-methylpentane, cyclohexane, n-heptane, and cycloheptane.

In another embodiment, additional compounds comprise hydrocarbonscontaining heteroatoms, such as dimethylether (DME, CH₃OCH₃. DME iscommercially available.

In another embodiment, additional compounds compriseiodotrifluoromethane (CF₃), which is commercially available from varioussources or may be prepared by methods known in the art.

In another embodiment, additional compounds comprise carbon dioxide(CO₂), which is commercially available from various sources or may beprepared by methods known in the art. In general, any suitableadditional compound can be employed so long as the amount of additionalcompound does not preclude the previously described partitioning of theinhibitor between the liquid phase fluoolefin and lubricant.

In another embodiment, the foregoing refrigerant compositions of thepresent invention are substantially free of additional compounds and, inparticular, substantially free of at least one of dimethyl ether, CF₃I,ammonia, and carbon dioxide. In one preferred aspect of this embodiment,the foregoing refrigerant compositions are substantially free of CF₃I.By “substantially free of additional compounds” it is meant that therefrigerant compositions as well as the inhibitor comprise less thanabout 10%, usually less than about 5% and in some cases 0% of theadditional compounds.

Of particular note are refrigerant compositions comprising HFO-1234yfand/or HFO-1234ze and additional compounds comprising: HFO-1225ye andHFC-32; HFO-1225ye and HFC-134a; HFO-1225ye, HFC-134a, and HFC-32;HFO-1225ye and HFO-1234yf; HFO-1225ye, HFC-32; HFO-1225ye, HFO-1225ye,and HFC-125. Further refrigerant compositions comprise a blend of atleast one of HFO-1234yf and HFO-1234ze as well as i) 134a, 32 and 125;ii) 134a; iii) 227ea; iv) 236fa; and v) 134.

In other embodiments of the invention, the fluoroolefin component of therefrigerant compositions comprises at least about 99 mass % HFO-1234yfand greater than 0 but less than 1 mass % of at least one memberselected from the group consisting of HFC-134a, HFO-1243zf, HFO-1225ye,HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-245cb andcombinations thereof.

In other embodiments of the invention, the fluoroolefin component of therefrigerant compositions comprises at least about 99 mass % HFO-1234zeand greater than 0 but less than 1 mass % of at least one memberselected from the group consisting of HFO-1234yf, HFC-245fa, HFC-236fa,HFO-1234ye and combinations thereof.

In other embodiments of the invention, the fluoroolefin component of therefrigerant compositions comprises one or more of the foregoingfluoroolefins that are blended with at least one hydrofluorocarbon.Examples of suitable hydrofluorocarbons comprise at least one memberselected from the group consisting of HFC-32, HFC-125, HFC-134a,HFC-152a, 236fa and HFC-227ea. The amount of hydrofluorocarbon can rangefrom about 25 to about 75, about 30 to about 60 and in some cases about30 to about 50. In one particular embodiment, the foregoing amounts ofhydrofluorocarbon are blended with at least one of HFO-1234yf andHFO-1234ze.

If desired, the blended composition can further comprise at least oneadditional member selected from the group consisting of HCC-40, HCFC-22,CFC-115, HCFC-124, HCFC-1122, and CFC-1113. The amount of the additionalmember can comprise greater than 0 to about 5 wt %, about 0 to about 2wt % and in some cases about 0 to about 0.5 wt %. In one particularembodiment, the foregoing amounts of additional members are blended withat least one of HFO-1234yf and HFO-1234ze. In another particularembodiment, the foregoing amounts of additional members are blended withat least one of HFO-1234yf and HFO-1234ze and at least onehydrofluorocarbon selected from the group consisting of HFC-32, HFC-125,HFC-134a, HFC-152a, 236fa and HFC-227ea, and in some cases, combinedwith carbon dioxide.

The lubricant component of the refrigerant compositions can comprisethose suitable for use with refrigeration or air-conditioning apparatus.Among these lubricants are those conventionally used in compressionrefrigeration apparatus utilizing chlorofluorocarbon refrigerants. Suchlubricants and their properties are discussed in the 1990 ASHRAEHandbook, Refrigeration Systems and Applications, chapter 8, titled“Lubricants in Refrigeration Systems”, pages 8.1 through 8.21, hereinincorporated by reference. Lubricants of the present invention maycomprise those commonly known as “mineral oils” in the field ofcompression refrigeration lubrication. Mineral oils comprise paraffins(i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons),naphthenes (i.e. cyclic or ring structure saturated hydrocarbons, whichmay be paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbonscontaining one or more rings characterized by alternating double bonds).Lubricants of the present invention further comprise those commonlyknown as “synthetic oils” in the field of compression refrigerationlubrication. Synthetic oils comprise alkylaryls (i.e. linear andbranched alkyl alkylbenzenes), synthetic paraffins and naphthenes,silicones, and poly-alpha-olefins. Representative conventionallubricants of the present invention are the commercially available BVM100 N (paraffinic mineral oil sold by BVA Oils), naphthenic mineral oilcommercially available under the trademark from Suniso® 3GS and Suniso®5GS by Crompton Co., naphthenic mineral oil commercially available fromPennzoil under the trademark Sontex 372LT, naphthenic mineral oilcommercially available from Calumet Lubricants under the trademarkCalumet® RO-30, linear alkylbenzenes commercially available from ShrieveChemicals under the trademarks Zerol® 75, Zerol® 150 and Zerol® 500 andbranched alkylbenzene, sold by Nippon Oil as HAB 22.

In another embodiment, the lubricant component of the present inventiverefrigerant compositions can comprise those which have been designed foruse with hydrofluorocarbon refrigerants and are miscible withrefrigerants and inhibitors of the present invention under compressionrefrigeration and air-conditioning apparatus' operating conditions. Suchlubricants and their properties are discussed in “Synthetic Lubricantsand High-Performance Fluids”, R. L. Shubkin, editor, Marcel Dekker,1993. Such lubricants include, but are not limited to, polyol esters(POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkyleneglycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Mich.),and polyvinyl ethers (PVEs).

Lubricants of the present invention are selected by considering a givencompressor's requirements and the environment to which the lubricantwill be exposed. The amount of lubricant can range from about 1 to about50, about 1 to about 20 and in some cases about 1 to about 3. In oneparticular embodiment, the foregoing refrigerant compositions arecombined with a PAG lubricant for usage in an automotive A/C systemhaving an internal combustion engine. In another particular embodiment,the foregoing refrigerant compositions are combined with a POE lubricantfor usage in an automotive A/C system having an electric or hybridelectric drive train.

The inhibitor has sufficient miscibility in the lubricant such that aportion of the inhibitor is present within the lubricant. The amount ofinhibitor present in the lubricant may vary when the refrigerantcomposition is employed as a working fluid or heat transfer medium.

In one embodiment of the invention, in addition to the inventiveinhibitor, the refrigerant composition can comprise at least oneadditive which can improve the refrigerant and air-conditioning systemlifetime and compressor durability are desirable. In one aspect of theinvention, the foregoing refrigerant compositions comprise at least onemember selected from the group consisting of acid scavengers,performance enhancers, and flame suppressants.

Additives which can improve the refrigerant and A/C lifetime andcompressor durability are desirable. In one aspect of the invention, theinventive refrigerant composition is used to introduce lubricant intothe A/C system as well as other additives, such as a) acid scavengers,b) performance enhancers, and c) flame suppressants.

An acid scavenger may comprise a siloxane, an activated aromaticcompound, or a combination of both. Serrano et al (paragraph 38 of US2011/0272624 A1), which is hereby incorporated by reference, disclosesthat the siloxane may be any molecule having a siloxyfunctionality. Thesiloxane may include an alkyl siloxane, an aryl siloxane, or a siloxanecontaining mixtures of aryl and alkyl substituents. For example, thesiloxane may be an alkyl siloxane, including a dialkylsiloxane or apolydialkylsiloxane. Preferred siloxanes include an oxygen atom bondedto two silicon atoms, i.e., a group having the structure: SiOSi. Forexample, the siloxane may be a siloxane of Formula IV:R1[Si(R2R3)4O]nSi(R2R3)R4, Where n is 1 or more. Siloxanes of Formula IVhave n that is preferably 2 or more, more preferably 3 or more, (e.g.,about 4 or more). Siloxanes of formula IV have n that is preferablyabout 30 or less, more preferably about 12 or less, and most preferablyabout 7 or less. Preferably the R4 group is an aryl group or an alkylgroup. Preferably the R2 groups are aryl groups or alkylgroups ormixtures thereof. Preferably the R3 groups are aryl groups or alkylgroups or mixtures thereof. Preferably the R4 group is an aryl group oran alkyl group. Preferably R1, R2, R3, R4, or any combination thereofare not hydrogen. The R2 groups in a molecule may be the same ordifferent. Preferably the R2 groups in a molecule are the same. The R2groups in a molecule may be the same or different from the R3 groups.Preferably, the R2 groups and R3 groups in a molecule are the same.Preferred siloxanes include siloxanes of Formula IV, wherein R1, R2, R3,R4, R5, or any combination thereof is a methyl, ethyl, propyl, or butylgroup, or any combination thereof. Exemplary siloxanes that may be usedinclude hexamethyldisiloxane, polydimethylsiloxane,polymethylphenylsiloxane, dodecamethylpentasiloxane,decamethylcyclo-pentasiloxane, decamethyltetrasiloxane,octamethyltrisiloxane, or any combination thereof.

Incorporated by previous reference from Serrano et al paragraph notesthat in one aspect of the invention, the siloxane is an alkylsiloxanecontaining from about 1 to about 12 carbon atoms, such ashexamethyldisiloxane. The siloxane may also be a polymer such aspolydialkylsiloxane, Where the alkyl group is a methyl, ethyl, propyl,butyl, or any combination thereof. Suitable polydialkylsiloxanes have amolecular weight from about 100 to about 10,000. Highly preferredsiloxanes include hexamethyldisiloxane, polydimethylsiloxane, andcombinations thereof. The siloxane may consist essentially ofpolydimethylsiloxane, hexamethyldisoloxane, or a combination thereof.

The activated aromatic compound may be any aromatic molecule activatedtowards a Friedel-Crafts addition reaction, or mixtures thereof. Anaromatic molecule activated towards a Friedel-Crafts addition reactionis defined to be any aromatic molecule capable of an addition reactionwith mineral acids. Especially aromatic molecules capable of additionreactions with mineral acids either in the application environment (ACsystem) or during the ASHRAE 97: 2007 “Sealed Glass Tube Method to Testthe Chemical Stability of Materials for Use within Refrigerant Systems”thermal stability test. Such molecules or compounds are typicallyactivated by substitution of a hydrogen atoms of the aromatic ring withone of the following groups: NH2, NHR, NRz, ADH, AD, NHCOCH3, NHCOR,4OCH3, OR, CH3, 4C2H5, R, or C6H5, where R is a hydrocarbon (preferablya hydrocarbon containing from about 1 to about 100 carbon atoms). Theactivated aromatic molecule may be an alcohol, or an ether, where theoxygen atom (i.e., the oxygen atom of the alcohol or ether group) isbonded directly to an aromatic group. The activated aromatic moleculemay be an amine Where the nitrogen atom (i.e., the nitrogen atom of theamine group) is bonded directly to an aromatic group. By way of example,the activated aromatic molecule may have the formula ArXRn, Where X is O(i.e., oxygen) or N (i.e., nitrogen); n:1 When X:O; n:2 When x:N; Ar isan aromatic group (i.e., group, C6H5); R may be H or a carbon containinggroup; and When n:2, the R groups may be the same or different. Forexample, R may be H (i.e., hydrogen), Ar, an alkyl group, or anycombination thereof, Exemplary activated aromatic molecules that may beemployed in a refrigerant composition according to the teachings hereininclude diphenyl oxide (i.e., diphenyl ether), methyl phenyl ether(e.g., anisole), ethyl phenyl ether, butyl phenyl ether or anycombination thereof. One highly preferred aromatic molecule activated toWards a Friedel-Crafts addition reaction is diphenyl oxide.

Incorporated by previous reference from Serrano et al. The acidscavenger (e.g., the activated aromatic compound, the siloxane, or both)may be present in any concentration that results in a relatively lowtotal acid number, a relatively low total halides concentration, arelatively low total organic acid concentration, or any combinationthereof. Preferably the acid scavenger is present at a concentrationgreater than about 0.0050 wt %, more preferably greater than about 0.05wt % and even more preferably greater than about 0.1 wt % (e.g. greaterthan about 0.5 wt %) based on the total weight of the refrigerantcomposition. The acid scavenger preferably is present in a concentrationless than about 3 wt %, more preferably less than about 2.5 wt % andmost preferably greater than about 2 wt % (e. g. less than about 1.8 wt%) based on the total Weight of the refrigerant composition.

Additional examples of acid scavengers which may be included in therefrigerant composition and preferably are excluded from the refrigerantcomposition include those described by Kaneko (U.S. patent applicationSer. No. 11/575,256, published as U.S. Patent Publication 2007/0290164,paragraph 42, expressly incorporated herein by reference), such as oneor more of: phenyl glycidyl ethers, alkyl glycidyl ethers,alkyleneglycolglycidylethers, cyclohexeneoxides, otolenoxides, or epoxycompounds such as epoxidized soybean oil, and those described by Singhet al. (U.S. patent application Ser. No. 11/250,219, published as20060116310, paragraphs 34-42, expressly incorporated herein byreference).

Preferred additives include those described in U.S. Pat. Nos. 5,152,926;4,755,316, which are hereby incorporated by reference. In particular,the preferred extreme pressure additives include mixtures of (A)tolyltriazole or substituted derivatives thereof, (B) an amine (e.g.Jeffamine M-600) and (C) a third component which is (i) an ethoxylatedphosphate ester (e.g. Antara LP-700 type), or (ii) a phosphate alcohol(e.g. ZELEC 3337 type), or (iii) a Zinc dialkyldithiophosphate (e.g.Lubrizol 5139, 5604, 5178, or 5186 type), or (iv) amercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-triadiaZolederivative (e. g. Curvan 826) or a mixture thereof. Additional examplesof additives which may be used are given in U.S. Pat. No. 5,976,399(Schnur, 5:12-6:51, hereby incorporated by reference).

Acid number is measured according to ASTM D664-01 in units of mg KOH/g.The total halides concentration, the fluorine ion concentration, and thetotal organic acid concentration is measured by ion chromatography.Chemical stability of the refrigerant system is measured according toASHRAE 97: 2007 (RA 2017) “Sealed Glass Tube Method to Test the ChemicalStability of Materials for Use within Refrigerant Systems”. Theviscosity of the lubricant is tested at 40° C. according to ASTM D-7042.

Mouli et al. (WO 2008/027595 and WO 2009/042847) teach the use of alkylsilanes as a stabilizer in refrigerant compositions containingfluoroolefins. Phosphates, phosphites, epoxides, and phenolic additivesalso have been employed in certain refrigerant compositions. These aredescribed for example by Kaneko (U.S. patent application Ser. No.11/575,256, published as U.S. Publication 2007/0290164) and Singh et al.(U.S. patent application Ser. No. 11/250,219, published as U.S.Publication 2006/0116310). All of these aforementioned applications areexpressly incorporated herein by reference.

Preferred flame suppressants include those described in patentapplication “Refrigerant compositions containing fluorine substitutedolefins CA 2557873 A1” and incorporated by reference along withfluorinated products such as HFC-125 and/or Krytox® lubricants, alsoincorporated by reference and described in patent application“Refrigerant compositions comprising fluoroolefins and uses thereofWO2009018117A1.”

The refrigerant compositions of the present invention may be prepared byany convenient method to combine the desired amount of the individualcomponents. A preferred method is to weigh the desired component amountsand thereafter combine the components in an appropriate vessel.Agitation may be used, if desired.

The present invention further relates to a process for producing coolingcomprising condensing a refrigerant composition comprising at least onefluoroolefin, at least one lubricant and an effective amount ofinhibitor, and thereafter evaporating said composition in the vicinityof a body to be cooled.

A body to be cooled may be any space, location or object requiringrefrigeration or air-conditioning. In stationary applications the bodymay be the interior of a structure, i.e. residential or commercial, or astorage location for perishables, such as food or pharmaceuticals. Formobile refrigeration applications the body may be incorporated into atransportation unit for the road, rail, sea or air. Certainrefrigeration systems operate independently with regards to any movingcarrier, these are known as “intermodal” systems. Such intermodalsystems include “containers” (combined sea/land transport) as well as“swap bodies” (combined road and rail transport).

The present invention further relates to a process for producing heatcomprising condensing a refrigerant composition comprising at least onefluoroolefin, at least one lubricant and an effective amount of aninhibitor comprising at least one of limonene and α-terpinene in thevicinity of a body to be heated, and thereafter evaporating saidcomposition.

A body to be heated may be any space, location or object requiring heat.These may be the interior of structures either residential or commercialin a similar manner to the body to be cooled. Additionally, mobile unitsas described for cooling may be similar to those requiring heating.Certain transport units require heating to prevent the material beingtransported from solidifying inside the transport container.

Another embodiment of the invention relates to a air-conditioning orrefrigeration apparatus comprising the foregoing refrigerantcompositions.

Another embodiment of the invention relates to storing the foregoingrefrigerant compositions in gaseous and/or liquid phases within a sealedcontainer wherein the oxygen and/or water concentration in the gasand/or liquid phases ranges from about 3 vol ppm to less than about3,000 vol ppm at a temperature of about 25° C., about 5 vol ppm to lessthan about 1,000 vol ppm and in some cases about 5 vol ppm to less thanabout 500 vol ppm.

The container for storing the foregoing refrigerant compositions can beconstructed of any suitable material and design that is capable ofsealing the refrigerant compositions therein while maintaining gaseousand liquids phases. Examples of suitable containers comprise pressureresistant containers such as a tank, a filling cylinder, and a secondaryfiling cylinder. The container can be constructed from any suitablematerial such as carbon steel, manganese steel, chromium-molybdenumsteel, among other low-alloy steels, stainless steel and in some case analuminum alloy. The container can include a pierce top or valvessuitable for dispensing flammable substances.

While any suitable method can be employed for preparing the inventiverefrigerant compositions, examples of such methods including blendingthe foregoing inhibitors with the foregoing fluoroolefin composition,purging lines and containers with a material comprising the inhibitor(e.g., an inhibitor with a nitrogen carrier, or the inventive stabilizedcomposition) and combining with a lubricant, among other suitablemethods.

In one embodiment, the inventive composition is prepared by adding theinhibitor to at least one of the fluoroolefin component and thelubricant, and then combining the fluorolefin component with thelubricant. In the event, the inhibitor is added to only one of thefluorolefin or lubricant and then the fluoroolefin and lubricant arecombined, the inhibitor will partition such that the inhibitor becomespresent in the fluoroolefin and lubricant. In another embodiment, theinhibitor can be added to a composition comprising at least onefluoroolefin component and at least one lubricant.

The following examples are provided to illustrate certain embodiments ofthe invention and shall not limit the scope of the appended claims.Example 1 illustrates the effectiveness of the inhibitor with afluoroolefin, Example 2 illustrates the effectiveness of the inhibitorwith a fluoroolefin and a lubricant, and Example 3 illustrates phaseequilibria and AC cycle performance with ternaryR-1234yf/d-limonene/lubricant (commercially available as POE32-3MAF)systems.

Example 1

A mixture of HFO-1234yf (30 g having at least 99.5 wt % purity*) andinitiator (and with and without inhibitor) was heated in a 210 mL shaketube at the temperature and for the period of time given in Table 4. Theshake tube was visually inspected for polymer formation as well as byusing NMR in accordance with conventional methods. Polymer can also bedetected by using conventional IR methods. *The HFO-1234yf comprised99.7 wt % HFO-1234yf, 1,000 ppm HFO-1234ze, 150 pp HFO-1225yeZ, 3 ppmtrifluoropropyne with the remainder comprising compounds that do notaffect the refrigeration performance of the mixture or activity of theinhibitor.

TABLE 4 concen. T polymer Examples Inhibitor (ppm) Initiator time (° C.)(wt %) Control-1 None air (3300 ppm) 2 weeks 75 0.003 1 d-limonene 50ppm air (3300 ppm) 2 weeks 75 N/D 2 d-limonene 100 ppm air (3300 ppm) 2weeks 75 N/D 3 α-terpinene 100 ppm air (3300 ppm) 2 weeks 75 N/DControl-2 None air (10,000 ppm) 2 weeks 100 2.8 4 d-limonene 500 ppm air(10,000 ppm) 2 weeks 100 <1 5 d-limonene 1000 ppm air (10,000 ppm) 2weeks 100 <1 6 α-terpinene 1000 ppm air (10,000 ppm) 2 weeks 100 <1Control-3 None cumene hydroperoxide 3 days 50 0.07 (1700 ppm) 7d-limonene 100 ppm cumene hydroperoxide 3 days 50 N/D (1700 ppm) 8α-terpinene 100 ppm cumene hydroperoxide 3 days 50 N/D (1700 ppm)Control-4 None air (3300 ppm) 2 weeks 150 0.05 9 d-limonene 100 ppm air(3300 ppm) 2 weeks 150 <0.003 10 d-limonene 200 ppm air (3300 ppm) 2weeks 150 N/D 11 α-terpinene 200 ppm air (3300 ppm) 2 weeks 150 N/DControl-5 None air (6600 ppm) 2 weeks 100 1.34 12 d-limonene 100 ppm air(6600 ppm) 2 weeks 100 <0.003 13 d-limonene 200 ppm air (6600 ppm) 2weeks 100 N/D 14 α-terpinene 200 ppm air (6600 ppm) 2 weeks 100 N/D 15α-terpinene + 200 ppm air (6600 ppm) 2 weeks 100 N/D butylatedhydroxytoluene 16 d-limonene + 200 ppm air (6600 ppm) 2 weeks 101 N/Dbutylated hydroxytoluene Control-6 None air (6600 ppm) 2 weeks 40 0.003Control-7 None air (10,000 ppm) 2 weeks 40 0.01 17 d-limonene 200 air(6600 ppm) 2 weeks 40 N/D 18 d-limonene 200 air (10,000 ppm) 2 weeks 40N/D 19 α-terpinene 200 air (6600 ppm) 2 weeks 40 N/D 20 α-terpinene 200air (10,000 ppm) 2 weeks 40 N/D 21 α-terpinene + 200 air (6600 ppm) 2weeks 40 N/D butylated hydroxytoluene 22 d-limonene + 200 air (10,000ppm) 2 weeks 40 N/D butylated hydroxytoluene

Example 2

A refrigerant blend comprising a mixture of HFO-1234yf (30 g having thecomposition of Example 1), at least one additional compound and aninitiator (and without inhibitor) was heated in a 210 mL shake tube atthe temperature and for the period of time given in Table 5. Examples1-6 evaluate an inhibitor with Opteon™ XP-10 refrigerant (R513a) and acommercially available lubricant. Examples 7-12 evaluate an inhibitorwith Opteon™ XP-40 refrigerant (R449a) and a commercially availablelubricant. Examples 13-18 evaluate an inhibitor with HFO-1234yf and acommercially available lubricant. XP10 refrigerant comprises 56 wt %HF1234yf and 44 wt % HFC-134 and XP10 refrigerant comprises 24.3 wt %R32, 24.7 wt % R125, 25.3 wt. %1234yf, and 25.7 wt %134a. XP10 and XP40refrigerants are commercially available from The Chemours Company. Theshake tube was visually inspected for polymer formation as well as byusing NMR. Data reported below is ppm by weight.

TABLE 5 concen. T polymer Examples Inhibitor (ppm) Lubricant InitiatorTime (° C.) (wt %) Control None air (2000 ppm) 2 weeks 135 0.003 1d-limonene 100 POE32-3MAF air (2000 ppm) 2 weeks 135 N/D 2 α-terpinene100 POE32-3MAF air (2000 ppm) 2 weeks 135 N/D 3 d-limonene 100 ND-11 air(2000 ppm) 2 weeks 135 N/D 4 α-terpinene 100 ND-11 air (2000 ppm) 2weeks 135 N/D 5 d-limonene 100 ND-12 air (2000 ppm) 2 weeks 135 N/D 6α-terpinene 100 ND-12 air (2000 ppm) 2 weeks 135 N/D Control None air(1000 ppm) 2 weeks 135 0.003 7 d-limonene 50 POE32-3MAF air (1000 ppm) 2weeks 135 N/D 8 α-terpinene 50 POE32-3MAF air (1000 ppm) 2 weeks 135 N/D9 d-limonene 50 ND-11 air (1000 ppm) 2 weeks 135 N/D 10 α-terpinene 50ND-11 air (1000 ppm) 2 weeks 135 N/D 11 d-limonene 50 ND-12 air (1000ppm) 2 weeks 135 N/D 12 α-terpinene 50 ND-12 air (1000 ppm) 2 weeks 135N/D Control None air (10,000) 2 weeks 100 2.8  13 d-limonene 100POE32-3MAF air (10,000) 2 weeks 100 N/D 14 α-terpinene 100 POE32-3MAFair (10,000) 2 weeks 100 N/D 15 d-limonene 100 ND-11 air (10,000) 2weeks 100 N/D 16 α-terpinene 100 ND-11 air (10,000) 2 weeks 100 N/D 17d-limonene 100 ND-12 air (10,000) 2 weeks 100 N/D 18 α-terpinene 100ND-12 air (10,000) 2 weeks 100 N/D

Example 3 Binary Phase Behavior

To analyze the phase behavior and d-limonene partitioning ofR-1234yf/d-limonene/lubricant (POE32-3MAF) systems, NRTL binaryinteraction parameters were fit to the following binary data:

-   -   1) R-1234yf/POE32-3MAF—VLE solubility data from −25 to 75° C.        were measured. The NRTL binary interaction parameters were fit        to VLE resulting in the prediction of VLLE, where liquid-liquid        phase splitting is predicted toward the R-1234yf rich side of        the composition domain. The fit quality is excellent, with a        deviation of 2.1% AARD from the data and is shown with the data        in FIG. 1.    -   2) R-1234yf/d-limonene—VLE bubble point data was measured at        50° C. and NRTL binary interaction parameters were fit to        experimental data fit to an accuracy of 2.1% AARD. In the        d-limonene-line region of composition space, negative deviations        from Raoult's Law are observed from 0 to about 9 mol-%        d-limonene, indicating that R-1234yf/d-limonene interactions are        stronger than R-1234yf/R-1234yf and d-limonene/d-imonene        interactions. This is not expected behavior and makes the        d-limonene activity more locally prevalent near liquid R-1234yf.        These data and model fit are shown in FIG. 2. The negative        deviations from Raoult's Law are shown in FIG. 3.    -   3) d-limonene/POE32-3MAP—was determined using computer software        based parameterization in order to calculate VLE behavior. The        calculated VLE is shown in FIG. 4.

Ternary Phase Behavior

Experimental bubble point pressures were experimentally measured atvarious POE32-3MAF contents with a binary mixture of 1000 ppm by weightd-limonene in R-1234yf. An NRTL model was used to calculate LLEs forthis ternary system. The binary interaction parameter data (shown inFIGS. 1-3) for R-1234yf/POE32-3MAF, d-limonene/POE32-3MAF andR-1234yf/d-limonene are then used to calculate the ternary phasebehavior of the R-1234yf/d-limonene/POE32-3MAF system, as shown in FIG.5.

The data and calculations shown in FIG. 1-5 can be employed to determinephase behavior (partitioning affects) and A/C performance of d-limonenefor amounts less than and greater than 1,000 ppm.

The data and calculations shown in FIGS. 1-5 also illustratevapor-liquid equilibria partitioning of d-limonene such that the vaporwill be R-1234yf substantially free of d-limonene and d-limonene willremain primarily in the liquid phases, either in the evaporator orcompressor oil sump, wherein the vapor circulating in an A/C system issubstantially free of d-limonene. As a result, d-limonene will not havea significant impact on the power efficiency or capacity of A/C systemsbecause the d-limonene will be predominately present in the liquidphases.

Although certain aspects, embodiments and principals have been describedabove, it is understood that this description is made only way ofexample and not as limitation of the scope of the invention or appendedclaims. The foregoing various aspects, embodiments and principals can beused alone and in combinations with each other.

What is claimed is:
 1. A refrigerant composition comprising at least one fluoroolefin, at least one lubricant and an effective amount of at least one inhibitor and wherein the composition is substantially free of oligomeric, homopolymers or other polymeric products.
 2. The composition of claim 1 wherein the composition comprises less than about 0.03 wt % of oligomeric, homopolymers or other polymeric products.
 3. The composition of claim 1 further comprising at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfatees.
 4. The composition of claim 3 wherein the inhibitor comprises at least one member selected from the group consisting of limomene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, benzene-1,4-diol.
 5. The composition of claim 3 further comprising at least one lubricant.
 6. The composition of claim 3 wherein the fluoroolefin comprises at least one member of HFO-1234yf and HFO-1234ze.
 7. The composition of claim 6 further comprising at least one member selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, HFC-227ea and carbon dioxide.
 8. The composition of claim 6 or 7 further comprising at least one member selected from the group consisting of HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-244bb and HFC-245cb.
 9. The composition of claim 6 or 7 further comprising at least one member selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113.
 10. The composition of claim 4 wherein the inhibitor is present in an amount of about 30 to about 3,000 ppm.
 11. The composition of claim 4 further comprising at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary-butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butaone, phenolics, bisphenol methane derivatives, and 2,2′-methylene bis (4-methyl-6-t-butyl phenol).
 12. The composition of claim 6 wherein the inhibitor comprises at least one of limonene and α-terpinene.
 13. The composition of claim 1 wherein the inhibitor comprises a liquid at a temperature of about −80 to 180° C.
 14. The composition of claim 1 further comprising at least one antioxidant.
 15. The composition of claim 6 further comprising at least one member selected from the group consisting of HFO-1225yeZ, HFO-1243zf, HFO-1234ze, HFC-236ea, HFC-245fa, and 3,3,3-trifluoropropyne.
 16. The composition of claim 15 wherein the member comprises HFO-1234ze, HFO-1225yeZ and 3,3,3-trifluoropropyne.
 17. The composition of claim 1 wherein the composition is substantially free of at least one of ammonia and CF3I.
 18. The composition of claim 1 wherein the composition consists essentially of HFO-1234yf and limonene and does not contain ammonia or CF3I.
 19. The composition of claim 15 wherein the composition consists essentially of HFO-1234yf, 3,3,3-trifluoropropyne and limonene.
 20. A refrigerant composition comprising at least one vapor phase fluoroolefin, at least one liquid phase fluoroolefin, at least one inhibitor and at least one lubricant wherein the inhibitor is present in the liquid phase fluoroolefin and the lubricant.
 21. The composition of claim 20 wherein the vapor phase fluoroolefin is substantially free of the inhibitor.
 21. The composition of claim 20 wherein the amount of inhibitor ranges from about 30 to about 3,000 ppm.
 22. A method for heating or cooling using the composition of claim
 20. 23. A container comprising the refrigerant composition of any of claims 1 through
 21. 